Repelling material for animals

ABSTRACT

A repelling material for animals retaining a great amount of a repellent and also having an excellent sustained release property can be obtained by adsorbing the repellent and at least one substance of phthalic acid esters, citric acid esters and glycols.

TECHNOLOGICAL FIELD

The invention relates to a repelling material for animals prepared byadsorbing an repellent on active carbon fiber.

BACKGROUND ART

As a repellent preventing animals from approaching, cinnamic aldehyde,γ-nonylolactone, rosegeranium oil, sandalwood oil, menthol, citral,cinnamic alcohol, methyleugenol, geraniol, linalool and the like areknown. In addition, limonene and the like are known as disclosed inJapanese Unexamined Patent Publication No. 110602/89.

As disclosed in the above-mentioned publication, said repellents wereapplied to an objective place in themselves or in the form ofpreparations with the addition of diluent, extending agent, retainingagent, excipient, emulsifier and the like by the following means:

(1) applying a repellent in a powder form.

(2) spraying a repellent in a liquid form.

(3) applying a repellent in a tablet form.

(4) filling a repellent in a capsule made of low airpermeable materialsuch as gelatin, polyvinylalcohol, maltose and the like and puting thecapsule at an objective place.

(5) adding a repellent in a bag made of polyethylene, polyvinylchloride,paper or the like and putting the bag at an objective place.

(6) putting a repellent in a film for bag-production by mixing arepellent into a melt of synthetic resin material.

(7) impregnating a repellent with paper and laminating one or two sidesof the paper with a film made of polyethylene and like synthetic resin.

A conventional repelling material for animals produced by retaining arepellent (e.g. repelling material for animals, birds and the like) on agranulated active carbon has only a short life so that development of arepelling material for animals retaining more amount of a repellent,gradually releasing the repellent and having a long life is earnestlydesired.

DISCLOSURE OF THE INVENTION

The inventors have conducted an extensive research on a repellingmaterial for animals retaining more amount of a repellent, graduallyreleasing the repellent and having a long life, found that a repellingmaterial for animals retaining more amount of a repellent, not rapidlyreleasing the retained repellent and having a long life can be producedby using special chemical substances as a sustained release agent, andaccomplish the invention.

Thus, the present invention relates to "a repelling material for animalsadsorbing at least one substance of phthalic acid esters, citric acidesters and glycols and an repellent on active carbon fiber".

As active carbon fibers, each fiber derived from pitch,polyacrylonitriles (PAN), phenols, celluloses and the like can be used.

The active carbon fiber is usually about 2 to about 3 μm in diameter offiber, about 500 to about 2500 m² /g in specific surface area, about 10to about 40 Å in diameter of pore, and distribution of pore size of theactive carbon fiber is sharp.

As a repellent, a variety of chemical substances can be selected inaccordance with a field of application.

In case of an animal repellent, the following chemical substances can beexemplified.

As repellents for dogs and cats, one or more of cinnamic aldehyde,γ-nonylolactone, lemon oil, paracresol acetate and the like can be used.

As repellents for pigeons, sparrows, bulbuls and like birds, one or moreof phenylethylalcohol, geraniol, rosegeranium oil (a general term ofbenzylbenzoate, linalylacetate, linalool etc.), spearmint oil,L-carvone, bornylacetate, camphor, tetrahydrothiophene, citronellol andthe like can be used.

As repellents for cockroaches, one or more of cinnamic alcohol,methyleugenol, geraniol and the like can be used.

As repellents for mosquitoes, one or more of sandalwood oil, menthol,citral and the like can be used.

However, a repelling material for animals has a short life by simplyretaining the repellent only on a carrier due to rapid release of therepellent in a short time. The inventors conducted a further extensiveresearch on a sustained release agent exerted an excellent sustainedrelease effect and found that phthalic acid esters, citric acid estersor glycols exerted a desired effect. The chemical substances exerting asustained release effect are exemplified such as: diethylphthalate,dibutylphthalate and the like being exemplified as esters of phthalicacid; triethylcitrate, trimethylcitrate and the like being exemplifiedas esters of citric acid; dipropylene glycol, butyldiglycol and the likebeing exemplified as glycols.

When not using a sustained release agent, active ingredients are rapidlyreleased while repelling material for animals is allowed to stand incontact with air. When content of the sustained release agent is toomuch, the effect as repelling material for animals becomes decreased.Thus, the quantity of a sustained release agent used is preferably 1 to9 parts by weight, more preferably 2.33 to 9 parts by weight per 1 partby weight of a repellent.

The active carbon fiber retaining an repellent in a variety of shapes,such as felt-like, a felt supported by polyester and like unwoven fabricin one or both sides, sheet-like, string-like, a component having ahigher bulk density formed by dry or wet process can be used.

The present repelling material for animals can be produced by dippingactive carbon fibers in a predetermined form with a mixed solution of arepellent and a sustained release agent, and impregnating and retaininga predetermined amount of the repellent and the sustained release agent.It can also be obtained by adding dropwise a mixed solution of arepellent and a sustained release agent to active carbon fibers.Further, it can be prepared by adsorbing a sustained release agent afteradsorbing a repellent on active carbon fibers, or by adsorbing arepellent after adsorbing a sustained release agent on active carbonfiber. Further, it can be obtained by adsorbing a repellent and asustained release agent on active carbon fiber alternately. In theseproducing methods, a method for adsorbing mixture of both substances ismore preferable.

The repelling material for animals formed by impregnating an repellentand a sustained release agent is used in an air-permeable bag or acontainer having a venting hole or an opening. The repelling materialfor animals is sealed so as not to releasing an active ingredient whenstored or carried. Diluent, extending agent, other sustained releaseagent not mentioned above, excipient, emulsifier and the like can beadditionally used, if necessary.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 indicates a result of determining a residual quantity of adsorbedmaterial while changing an amount of DEP (diethylphthalate) used inconditions that the repelling material produced by impregnating a 0.5 gof active carbon fiber with a mixture of a repellent and DEP(diethylphthalate) until saturated is allowed to stand in a thermostatat 60° C.

FIG. 2 indicates a result of determining a residual quantity of adsorbedmaterial while changing a kind of a sustained release agent used inconditions that the repelling material produced by impregnating a 0.5 gof active carbon fiber with a mixture of a repellent and a sustainedrelease agent until saturated is allowed to stand in a thermostat at 60°C.

FIG. 3 indicates a result of determining a residual quantity of adsorbedmaterial while changing a kind of a sustained release agent used inconditions that the repelling material produced by impregnating a 0.5 gof active carbon fiber or a 0.5 g of granulated active carbon with amixture of a repellent and a sustained release agent until saturated isallowed to stand in a thermostat at 60° C.

FIG. 4 indicates a result of determining a residual quantity of adsorbedmaterial in conditions that the repellent produced by impregnating a 0.5g of active carbon fiber with only a repellent until saturated isallowed to stand in a thermostat at 60° C.

FIG. 5 indicates a result of determining a residual quantity of adsorbedmaterial after 7 days while changing an amount of a sustained releaseagent,

FIG. 6 indicates a result of determining a residual quantity of adsorbedmaterial when a 1.0 g of active carbon fiber mixed unwoven fabric madeof nylon and polyester and filter paper adsorbs a repellent and asustained release agent until saturated.

FIG. 7 indicates a sectional drawing of active carbon fiber supported byunwoven fabric made of polyester fiber.

FIG. 8 shows repelling material for animals stored in a can.

BEST MODE OF CARRYING OUT THE INVENTION EXAMPLE

The present invention is described in detail based on examples, however,the invention is not limited to the examples.

Active carbon fiber used in experiments or examples is the active carbonfiber from pitch (product of OSAKA GAS CHEMICAL CO., LTD.) having aspecific surface area of 1,000 m² /g. A repellent used in experiments 1to 4 is the repellent for birds in a mixture of four species ofphenylethylalcohol, geraniol, citronellol and rosegeranium oil.

EXPERIMENT 1

A 0.5 g of active carbon fiber was dipped and impregnated with a mixtureof 90 parts by weight of DEP (diethylphthalate) as a sustained releaseagent and 10 parts by weight of the repellent until saturated. Aftersuspending the active carbon fiber taken out from the mixture andthreaded for 1 hour at room temperature, the adsorbed material wasweighed with a balance. The weight was defined as a initial weight. Theactive carbon fiber impregnated with the mixture was allowed to stand ina thermostat at 60° C. to accelerate release of adsorbed substances andmeasured changes of the weight (a value calculated by subtracting aweight of the fiber from the total weight, i.e., a residual quantity ofadsorbed substances) of the fiber with time. The results of themeasurement are shown as curve A in FIG. 1.

FIG. 1 also disclose data described as B, C, D and E when changing theproportion of DEP and the repellent to 80:20, 70:30, 60:40 and 50:50respectively.

It is clear that using smaller amount of DEP causes considerablereduction of weight of the repelling material and that a life of therepelling material for animals becomes shorter.

EXPERIMENT 2

A 0.5 g of active carbon fiber was dipped and impregnated with a mixtureof 80 parts by weight of TEC (triethyl citrate) as a sustained releaseagent and 20 parts by weight of the repellent until saturated. Aftersuspending the active carbon fiber taken out from the mixture andthreaded for 1 hour at room temperature, the weight of adsorbed material(initial weight) was determined with a balance. The active carbon fiberimpregnated with the mixture was allowed to stand in a thermostat at 60°C. and measured changes of the weight of the fiber. The results of themeasurement are shown as curve F in FIG. 2.

FIG. 2 also discloses changes of weights as curves G and H when usingDPG (dipropyleneglycol) and ethanol as a sustained release agent. Theproportion of the repellent and the sustained release agent is 20:80 inall cases. In addition, data of experiment 1 that the proportion of therepellent and DEP (diethyl phthalate) is 20:80 are also shown as curveB.

It is clear that DEP, TEC and DPG has a sustained release effect in thissequence, and that ethanol can hardly be expected in a sustained releaseeffect because most of adsorbed material was released in one day.

EXPERIMENT 3

Using commercially available granulated active carbon from coconut huskhaving a specific surface area of 480 m² /g as a carrier, a 0.5 g ofgranulated active carbon was dipped and impregnated with a mixture of 80parts by weight of DEP as a sustained release agent and 20 parts byweight of the repellent until saturated. After suspending the granulatedactive carbon taken out from the mixture and threaded for 1 hour at roomtemperature, the weight of the adsorbed material (initial weight) wasdetermined with a balance. The granulated active carbon impregnated withthe mixture was allowed to stand in a thermostat at 60° C. and measuredchanges of the weight. The results of the measurement are shown as curveI in FIG. 3.

FIG. 3 also discloses changes of weight described as curve J when usingethanol as a sustained release agent. The weight proportion of therepellent and the sustained release agent is 20:80. Additional data areshown as curve B when the proportion of a repellent and a sustainedrelease agent, DEP, is 20:80 in experiment 1, further data are shown ascurve H when the proportion of the repellent and sustained releaseagent, ethanol, is 20:80.

Although the specific surface area of granulated active carbon is 48% ofthe specific surface area of active carbon fiber, a retained quantity ofthe mixture of DEP and the repellent is only 3.4% of that of the activecarbon fiber. Further, the active carbon fiber retained 89% of theinitial weight after 7 days. In contrast, the granulated active carboncan retain adsorbed material as low as 28% of the initial weight.

The experiment clearly shows that using DEP as a sustained release agentwith granulated active carbon hardly exerts a sustained release effect,and that using DEP as a sustained release agent with active carbon fiberexerts a considerable sustained release effect due to synergistic actionwith the active carbon fiber and DEP. This will be caused by that theactive carbon fiber has different pore distributions and adsorptionproperties from those of granulated active carbon.

EXPERIMENT 4

To inspect an essential amount of the sustained release agent, anexperiment was conducted without using any sustained release agent.

A 0.5 g of active carbon fiber was dipped in a solution consisting ofonly the repellent and impregnated with the solution until saturated.After suspending the active carbon fiber taken out from the solution andthreaded for 1 hour at room temperature, the weight of the adsorbedmaterial (initial weight) was determined with a balance. The activecarbon fiber impregnated with the solution was allowed to stand in athermostat at 60° C. and measured changes of the weight of the fiber.The results of the measurement are shown as curve Z in FIG. 4.

FIG. 5 illustratively indicates a proportion of a residual quantity ofadsorbed material on the repellent material corresponding to A, B, C, Dand E in FIG. 1 after seven days and a residual quantity of adsorbedmaterial on the repellent material corresponding to Z in FIG. 4 afterseven days based on the initial weight of the adsorbed quantityrespectively. FIG. 5 shows that 50 or more % (at least 1 part by weightof the sustained release agent per 1 part by weight of the repellent) ofcontent of sustained release agent is necessary, if evaluation standardis determined whether a residual quantity is twice as much as thequantity of residue without using a sustained release agent.

EXPERIMENT 5

A 1 g of carriers are produced by using (1) active carbon fiber frompitch supported by unwoven fabric made of polyester in both sides(product of OSAKA GAS CHEMICAL CO., LTD., Commodity code: FN200PS10)having a weight per unit area of 200 g/m² and a specific surface area of1,000 m² /g, (2) mixed unwoven fabric made of nylon and polyester, and(3) filter paper respectively. After these carriers were dipped in amixture of 20 parts by weight of the repellent for pegions produced bymixing 4 speices, phenyl ethylalcohol, geraniol, citronellol androsegeranium oil, and 80 parts by weight of diethyl phthalate as asustained release agent, the carriers being allowed to suspend for 1hour at room temperature (15° C.), the adsorbed material being weighed.Each adsorbed amount of carriers is 12.57 g in active carbon fibercarrier from pitch, 4.24 g in unwoven fabric carrier made of polyesterand 0.88 g in filter paper carrier.

The samples were allowed to stand on a beaker in a thermostat at 60° C.and measured changes of the weight of the adsorbed material with time toobtain a graphic chart shown in FIG. 6.

Although the carrier from filter paper (shown as "C") and the carrierfrom mixed unwoven fabric made of nylon and polyester (shown as "B")lost all of repellent for birds by volatilization after 5 days and 8days respectively, the carrier from unwoven fabric of active carbonfiber (shown as "A") still retained and adsorbed as much as about 3 g ofthe repellent for birds after 18 days.

It is clear that the active carbon fiber is better than mixed unwovenfabric made of nylon and polyester and filter paper in both adsorbedamount and a sustained release property as a carrier for a repellingmaterial.

EXAMPLE 1

A solution for producing repelling material for birds were prepared byadding 80 parts by weight of diethylphthalate to 20 parts by weight of arepellent solution for birds containing about 58% ofβ-phenylethylalcohol, about 17% of citronellol, about 13% ofbenzylbenzoate, about 6% of geraniol, about 4% of linarylacetate andabout 2% of lynalool.

Piled were two pieces of unwoven fabric of the active carbon fiber(product of OSAKA GAS CHEMICAL CO., LTD., Commodity Code: FN300PS) shownin FIG. 7 having a weight per unit area of about 300 g/m² (5 to 8 mm inthickness) as active carbon fiber obtained monolithically by conductingneedle-punch after piled on both sides of active carbon fiber having aspecific surface area of 1,000 g/m², and then about 4.3 mm×about 4.3 mmof a small piece (weight=1 g) of active carbon fiber was cut out, and a10 g of the repellent solution for birds was added dropwise to the pieceto adsorb the repellent.

After the obtained sample 3 was put in a container 4 made of metalhaving an inner diameter of 50 mm and a height of 27 mm, an inner lid 5formed twelve opening 7 having a diameter of seven mm was put on thecontainer, and the container was canned and sealed with can-formingdevice to produce a transferable can storing repellent material forbirds.

After the sealed can storing the repellent for birds was allowed tostand for 1 month, the cover 6 was opened and the can was suspended at atree where birds (pigeons, sparrows, bulbuls, etc) came flying in thepark for 2 months to observe an effect of the repelling material. Birds(pegion, sparrow, bulbul, etc.) did not approach the tree suspending thecan within a 10-meter radius from the tree, however birds came againflying around the tree after 3 weeks. This demonstrates that the presentrepellent is effective to avoid birds, in particular, pigeons, sparrows,bulbuls, etc.

EXAMPLE 2

A repellent solution was prepared by adding 80 parts by weight ofdiethyl phthalate to a 20 g of phenylethylalcohol. The solution wasadsorbed on a 1 g of active carbon fiber in the same manner as inexample 1, putting the fiber in the can shown in FIG. 8, sealing thecan, opening the can after 1 month, and suspending the can at a tree inthe park where birds (pigeons, sparrows, bulbuls, etc.) came flying.Birds did not become approaching the tree. However, birds becomeapproaching the tree again after 3 weeks.

This demonstrates that DEP can be used to the repellent whosecomposition is different from that of example 1.

EXAMPLE 3

A repelling perfume for dogs and cats was prepared by mixing about 34parts by weight of cinnamic aldehyde, about 6 parts by weight ofγ-nonylolactone, about 57 parts by weight of limonene (major componentof lemon oil) and 3 parts by weight of paracresolacetate, and a mixedsolution of 20 parts by weight of this mixture and 80 parts by weight ofdiethylphthalate was prepared. To this mixture, the active carbon fiberused in experiment 5 was dipped, and the repellent for animal wasadsorbed and retained on the active carbon fiber to give repellentmaterial for dogs and cats.

This repelling material for animals was put near the garbage where catsoften searched about for food to observe an effect of the repellingmaterial.

Before placing the repellent, cats have gathered around the gabbage andbrought down the gabbage to scatter about rubbish. However, after therepellent material was allowed to stand, cats did not approach thegabbage so that the place was kept clean., The effect continued for 3weeks after placing the repelling material for animal.

Further, a 1 g of the active carbon fiber used in example 5 was dippedin a solution produced by dissolving 20 parts by weight of limonene in80 parts by weight of diethylphthalate to give the repelling materialfor animals used for dogs and cats.

This repelling material for animals was put near the garbage where catsoften searched about for food to observe an effect of the repellingmaterial. An effect of the repelling material continued for 2 weeks.This assured that DPE is effective as a sustained release agent when therepellent is composed of only limonene.

INDUSTRIAL APPLICABILITY

When at least one substance of phthalic acid esters, citric acid estersand glycols was adsorbed and retained on active carbon fiber, a greatamount of repellent can be adsorbed and retained, and also the repellentis gradually released to a high degree so that an excellent repellingmaterial for animals being capable of using for a long time can beobtained.

We claim:
 1. An article of manufacture comprising active carbon fiberimpregnated with a repellant for animals and as a sustained releaseagent a substance selected from the group consisting of phthalic acidesters, citric acid esters and glycols.
 2. The article of manufactureaccording to claim 1 wherein the phthalic acid esters arediethylphthalate or dibutylphthalate, the citric acid esters are"triethylcitrate or trimethylcitrate and the glycols aredipropyleneglycol or butyldiglycol.
 3. The article of manufactureaccording to claim 1 wherein a total amount of phthalic acid esters,citric acid esters and glycols is in the range of 1 to 9 parts by weightper 1 part by weight of a repellent.
 4. The article of manufactureaccording to claim 1 wherein the repellent is a repellent for birds.